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高电活性噻唑鎓[5,4-d]噻唑-2,5-二羧酸-银电化学发光金属有机框架:合成、性质及其在谷胱甘肽检测中的应用

Highly electroactive thiazolium [5,4-d]thiazol-2,5-dicarboxylic acid-silver electrochemiluminescent metal-organic frameworks: synthesis, properties and application in glutathione detection.

作者信息

Yu Ru, Zhang Haoran, Tu Ying, Nie Fei

机构信息

Key Laboratory of Synthetic and Natural Functional Molecule Chemistry (Ministry of Education), College of Chemistry & Materials Science, Northwest University, Xi' an, 710069, PR, China.

出版信息

Mikrochim Acta. 2025 Jan 14;192(2):75. doi: 10.1007/s00604-024-06948-3.

DOI:10.1007/s00604-024-06948-3
PMID:39805989
Abstract

Thiazolo[5,4-d]thiazole-2,5-dicarboxylic acid (HThz), a thiazolothiazole (TTz) derivative with carboxylic acid groups, was synthesized as a ligand for the creation of five MOFs, each associated with distinct metal ions including Ag, Mn, Co, Zn, and Cu. The cathodic electrochemiluminescence (ECL) of HThz and the resulting MOFs was investigated. HThz was found to generate ECL signals, but this process was heavily reliant on potassium persulfate (KSO) as a co-reactant. However, the Ag-MOF, formed with HThz as the ligand, exhibited substantial ECL signals without the need for any co-reactant, which is different from other metal-containing MOFs. The smaller band gap, higher electron mobility and the unique electrocatalytic activity of Ag ions were confirmed to be the reasons for the excellent ECL performance of Ag-MOF. The interaction between thiol group of glutathione (GSH) and Ag-MOF suppressed the ECL signal of the Ag-MOF-KSO system. Based on this, a sensitive ECL method for GSH was developed and effectively utilized for GSH quantification in cell lysates.

摘要

噻唑并[5,4-d]噻唑-2,5-二羧酸(HThz)是一种带有羧酸基团的噻唑并噻唑(TTz)衍生物,被合成作为一种配体用于制备五种金属有机框架(MOF),每种MOF与包括银(Ag)、锰(Mn)、钴(Co)、锌(Zn)和铜(Cu)在内的不同金属离子相关联。对HThz以及由此产生的MOF的阴极电化学发光(ECL)进行了研究。发现HThz能产生ECL信号,但这个过程严重依赖过硫酸钾(KSO)作为共反应剂。然而,以HThz作为配体形成的Ag-MOF在不需要任何共反应剂的情况下表现出强烈的ECL信号,这与其他含金属的MOF不同。银离子较小的带隙、较高的电子迁移率和独特的电催化活性被确认为是Ag-MOF具有优异ECL性能的原因。谷胱甘肽(GSH)的巯基与Ag-MOF之间的相互作用抑制了Ag-MOF-KSO体系的ECL信号。基于此,开发了一种用于GSH的灵敏ECL方法,并有效地用于细胞裂解物中GSH的定量分析。

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